CN112300079B - N-difluoromethyl azole selenourea derivative or pharmaceutically acceptable salt and application thereof - Google Patents

N-difluoromethyl azole selenourea derivative or pharmaceutically acceptable salt and application thereof Download PDF

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CN112300079B
CN112300079B CN202011222204.1A CN202011222204A CN112300079B CN 112300079 B CN112300079 B CN 112300079B CN 202011222204 A CN202011222204 A CN 202011222204A CN 112300079 B CN112300079 B CN 112300079B
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acid
alkyl
compound
difluoromethyl
selenourea
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CN112300079A (en
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汤日元
郭雪莹
黄子豪
徐汉虹
熊兰图
魏林豪
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South China Agricultural University
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    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07D473/00—Heterocyclic compounds containing purine ring systems
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    • C07D473/32—Nitrogen atom
    • C07D473/34—Nitrogen atom attached in position 6, e.g. adenine

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Abstract

The invention discloses an N-difluoromethyl azole selenourea derivative or an agropharmaceutically acceptable salt and application thereof. The structure of the N-difluoromethyl azole selenourea derivative is shown as a general formula (I) or a general formula (II), and the definition of each substituent group in the formula is shown in the specification. The compound of the general formula (I) or the general formula (II) has insecticidal activity on pests in agriculture, forestry and other fields, and meanwhile, the compound of the general formula (I) or the general formula (II) is used as an insecticide, namely, the compound of the general formula (I) or the general formula (II) is used for preparing medicines for controlling the pests in agriculture, forestry or other fields. In particular to Lepidoptera (Lepidoptera) mouth such as plutella xylostella (Plutella xylostella), spodoptera frugiperda (Spodoptera frugiperda), spodoptera exigua (S.exigua) and spodoptera litura (S.litura)Chewing insect pests have excellent insecticidal activity.

Description

N-difluoromethyl azole selenourea derivative or pharmaceutically acceptable salt and application thereof
Technical Field
The invention belongs to the field of agricultural pesticides, and particularly relates to an N-difluoromethyl azole selenourea derivative or an agropharmaceutically acceptable salt and application thereof.
Background
The nitrogen heterocyclic pesticide has the advantages of high insecticidal activity, broad spectrum, low toxicity and the like, and has become an advantageous skeleton for the creation of new pesticides. In recent years, newly developed pesticides such as cycloxaprid, cyantraniliprole, sulfoxaflor, fluopyram, cyflumetofen, spirotetramat and flucyrilin are all nitrogen heterocyclic derivatives, and are mainly obtained by being derived from nitrogen heterocycles such as pyrazole or pyridine. However, the problems of serious drug resistance and exchange resistance caused by long-term use of the existing pesticide increase the difficulty in pest control. Particularly, the serious insect pests such as plutella xylostella (Plutella xylostella), spodoptera frugiperda (Spodoptera frugiperda), spodoptera exigua (S.exigua), spodoptera litura (S.litura) and meloidogyne incognita (Meloidogyne incognita) generate serious resistance. There is an urgent need to develop new target pesticides with high efficiency and low toxicity to solve the current resistance problem. The key point of the creation of new pesticides is to find out a new skeleton of the pesticide with a new action target point.
The azole compound has the advantages of changeable structure, high selectivity, high efficiency, low toxicity and the like, accords with the development concept and the requirement of modern green pesticides, and becomes an advantageous skeleton for the creation of new pesticides. In the early stage, the research shows that the benzimidazolone derivative has insecticidal activity on plutella xylostella, spodoptera frugiperda, spodoptera exigua and spodoptera exigua (patent application number: 202010743473.6), wherein the insecticidal activity effect of the benzimidazolone is better. On the basis, the fluorine-containing group is designed to enhance the activity of the compound, and when difluoromethyl is introduced, the fluorine-containing group has obvious influence on the pharmacokinetic properties of the drug, namely membrane permeability, bioavailability, binding affinity, metabolic stability and lipophilicity. According to the analysis of the prior publications, the N-difluoromethyl selenourea derivatives are not applied to insecticidal application, and related reports are not disclosed that the compounds have insecticidal activity on plutella xylostella, spodoptera frugiperda, asparagus caterpillar and prodenia litura.
Disclosure of Invention
In order to develop novel pesticide lead compounds, the primary object of the invention is to provide an N-difluoromethyl azole selenourea derivative or an agropharmaceutically acceptable salt which can control various agricultural and forestry pests and sanitary pests.
Another object of the present invention is to provide the use of the above-mentioned N-difluoromethyl azole selenourea derivatives or agropharmaceutically acceptable salts for the preparation of a medicament for controlling pests in agriculture or other fields.
The invention aims at realizing the following technical scheme:
the structure of the N-difluoromethyl azole selenourea derivative for preventing and controlling agricultural and forestry pests or pests in other fields is shown as a general formula (I) or a general formula (II);
the preferable technical scheme of the invention is as follows: in the general formula (I) or (II)
X is selected from C, N; y is selected from C, N;
R 1 selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, ethyl fluoroacetate, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl, C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkoxy, C 3 -C 12 Cycloalkyl, halo C 3 -C 12 Cycloalkyl, C 2 -C 12 Alkenyl, C 2 -C 12 Alkynyl, C 2 -C 12 Alkenyloxy, haloC 2 -C 12 Alkenyloxy, C 2 -C 12 Alkynyloxy groupHalogenated C 2 -C 12 Alkynyloxy, C 1 -C 12 Alkylthio, halo C 1 -C 12 Alkylthio, C 1 -C 12 Alkoxy C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxy C 1 -C 12 Alkyl, C 1 -C 12 Alkylthio C 1 -C 12 Alkyl, halo C 1 -C 12 Alkylthio C 1 -C 12 Alkyl, sulfinyl-containing C 1 -C 12 Alkyl, C containing halogenated and sulfinyl groups 1 -C 12 Alkyl, containing sulfonyl C 1 -C 12 Alkyl, halogeno and sulphonyl C 1 -C 12 Alkyl containing amino groups C 1 -C 12 Alkyl, amino-containing halogenated C 1 -C 12 Alkyl, C 1 -C 12 Alkoxycarbonyl, CONH 2 ，C 1 -C 12 Alkylaminocarbonyl, di (C) 1 -C 12 Alkyl) aminocarbonyl, cyano C 1 -C 12 Alkoxy, C 1 -C 12 Alkoxycarbonyl group C 1 -C 12 Alkyl, C 1 -C 12 Alkylaminocarbonyl group C 1 -C 12 Alkyl, di (C) 1 -C 12 Alkyl) aminocarbonyl C 1 -C 12 An alkyl group; or benzyl, pyridine methylene, pyrimidine methylene, thiazole methylene, thiophene methylene, furan methylene, pyrazole methylene; or phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more hetero atoms such as oxygen, sulfur, nitrogen, and the substituent can be C 1 -C 12 Alkyl, C of (2) 1 -C 12 Alkoxy, C 1 -C 12 Alkylmercapto, C 1 -C 12 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C 1 -C 12 Alkoxyacyl, C 1 -C 12 An acyloxy group;
R 2 the substituent groups in any position shown in the general formula (I) or (II) can be monosubstituted, disubstituted or trisubstituted of the same or different groups;
R 2 selected from hydrogen, C 1 -C 12 Alkyl, C of (2) 1 -C 12 Alkoxy, C 1 -C 12 Alkylmercapto, C 1 -C 12 Alkylamino, C 1 -C 12 Alkoxyacyl, C 1 -C 12 Acyloxy, halogeno C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkylmercapto, halo C 1 -C 12 Alkylamino, halo C 1 -C 12 Alkoxyacyl, halo C 1 -C 12 Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide or aryl containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more hetero atoms such as oxygen, sulfur, nitrogen, and the substituent can be C 1 -C 12 Alkyl, C of (2) 1 -C 12 Alkoxy, C 1 -C 12 Alkylmercapto, C 1 -C 12 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C 1 -C 12 Alkoxyacyl, C 1 -C 12 An acyloxy group.
The further preferable technical scheme of the invention is as follows: in the general formula (I) or (II)
X is selected from C, N; y is selected from C, N;
R 1 selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, ethyl fluoroacetate, C 1 -C 8 Alkyl, halo C 1 -C 8 Alkyl, C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkoxy, C 3 -C 8 Cycloalkyl, halo C 3 -C 8 Cycloalkyl, C 2 -C 8 Alkenyl, C 2 -C 8 Alkynyl, C 2 -C 8 Alkenyloxy, haloC 2 -C 8 Alkenyloxy, C 2 -C 8 Alkynyloxy, halogenated C 2 -C 8 Alkynyloxy, C 1 -C 8 Alkylthio, halo C 1 -C 8 Alkylthio, C 1 -C 8 Alkoxy C 1 -C 8 Alkyl, halo C 1 -C 8 Alkoxy C 1 -C 8 Alkyl, C 1 -C 8 Alkylthio C 1 -C 8 Alkyl, halo C 1 -C 8 Alkylthio C 1 -C 8 Alkyl, sulfinyl-containing C 1 -C 8 Alkyl, C containing halogenated and sulfinyl groups 1 -C 8 Alkyl, containing sulfonyl C 1 -C 8 Alkyl, halogeno and sulphonyl C 1 -C 8 Alkyl containing amino groups C 1 -C 8 Alkyl, amino-containing halogenated C 1 -C 8 Alkyl, C 1 -C 8 Alkoxycarbonyl, CONH 2 ，C 1 -C 8 Alkylaminocarbonyl, di (C) 1 -C 8 Alkyl) aminocarbonyl, cyano C 1 -C 8 Alkoxy, C 1 -C 8 Alkoxycarbonyl group C 1 -C 8 Alkyl, C 1 -C 8 Alkylaminocarbonyl group C 1 -C 8 Alkyl, di (C) 1 -C 8 Alkyl) aminocarbonyl C 1 -C 8 Alkyl, or phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
aryl groups may be phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other moieties containing one or more hetero atoms such as oxygen, sulfur, nitrogen, and the likeHeteroaryl, the substituents may be C 1 -C 8 Alkyl, C of (2) 1 -C 8 Alkoxy, C 1 -C 8 Alkylmercapto, C 1 -C 8 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C 1 -C 8 Alkoxyacyl, C 1 -C 8 An acyloxy group;
R 2 the substituent group in any position shown in the general formula (I) or (II) can be monosubstituted, disubstituted or trisubstituted of the same or different groups;
R 2 selected from hydrogen, C 1 -C 8 Alkyl, C of (2) 1 -C 8 Alkoxy, C 1 -C 8 Alkylmercapto, C 1 -C 8 Alkylamino, C 1 -C 8 Alkoxyacyl, C 1 -C 8 Acyloxy, halogeno C 1 -C 8 Alkyl, halo C 1 -C 8 Alkoxy, halo C 1 -C 8 Alkylmercapto, halo C 1 -C 8 Alkylamino, halo C 1 -C 8 Alkoxyacyl, halogen C 1 -C 8 Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide or aryl containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more hetero atoms such as oxygen, sulfur, nitrogen, and the substituent can be C 1 -C 8 Alkyl, C of (2) 1 -C 8 Alkoxy, C 1 -C 8 Alkylmercapto, C 1 -C 8 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C 1 -C 8 Alkoxyacyl, C 1 -C 8 An acyloxy group.
The invention further preferably adopts the technical scheme that: in the general formula (I) or (II)
X is selected from C, N; y is selected from C;
R 1 selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, ethyl fluoroacetate, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, halo C 1 -C 6 Alkoxy, C 3 -C 6 Cycloalkyl, halo C 3 -C 6 Cycloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Alkenyloxy, haloC 2 -C 6 Alkenyloxy, C 2 -C 6 Alkynyloxy, halogenated C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylthio, halo C 1 -C 6 Alkylthio, C 1 -C 6 Alkoxy C 1 -C 6 Alkyl, halo C 1 -C 6 Alkoxy C 1 -C 6 Alkyl, C 1 -C 6 Alkylthio C 1 -C 6 Alkyl, halo C 1 -C 6 Alkylthio C 1 -C 6 Alkyl, sulfinyl-containing C 1 -C 6 Alkyl, C containing halogenated and sulfinyl groups 1 -C 6 Alkyl, containing sulfonyl C 1 -C 6 Alkyl, halogeno and sulphonyl C 1 -C 6 Alkyl containing amino groups C 1 -C 6 Alkyl, amino-containing halogenated C 1 -C 6 Alkyl, C 1 -C 6 Alkoxycarbonyl, CONH 2 ，C 1 -C 6 Alkylaminocarbonyl, di (C) 1 -C 6 Alkyl) aminocarbonyl, cyano C 1 -C 6 Alkoxy, C 1 -C 6 Alkoxycarbonyl group C 1 -C 6 Alkyl, C 1 -C 6 Alkylaminocarbonyl group C 1 -C 6 Alkyl, di (C) 1 -C 6 Alkyl) aminocarbonyl C 1 -C 6 Alkyl, or phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or the likeIs an aryl group containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more hetero atoms such as oxygen, sulfur, nitrogen, and the substituent can be C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 1 -C 4 Alkylmercapto, C 1 -C 4 Alkylamino, C 1 -C 4 Alkoxyacyl, C 1 -C 4 Acyloxy, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl;
R 2 the substituent group at any position on the aromatic ring shown in the general formula (I) or (II) can be monosubstituted, disubstituted or trisubstituted of the same or different groups; r is R 3 Selected from hydrogen, C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 1 -C 4 Alkylmercapto, C 1 -C 4 Alkylamino, C 1 -C 4 Alkoxyacyl, C 1 -C 4 Acyloxy, halogeno C 1 -C 4 Alkyl, halo C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkylmercapto, halo C 1 -C 4 Alkylamino, halo C 1 -C 4 Alkoxyacyl, halogen C 1 -C 4 Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide or aryl containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more hetero atoms such as oxygen, sulfur, nitrogen, and the substituent can be C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 1 -C 4 Alkylmercapto, C 1 -C 4 Alkylamino, fluorine, chlorine,Bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, C 1 -C 4 Alkoxyacyl, C 1 -C 4 An acyloxy group.
The invention still further preferably adopts the technical scheme that: in the general formula (I) or (II)
X is selected from C; y is selected from C;
R 1 selected from hydrogen, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, dibromomethyl, tribromomethyl, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, halo C 3 -C 6 Cycloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkynyl, C 1 -C 6 Ester group, C 1 -C 6 Acetoxy group, C 1 -C 6 Cyano, either phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more hetero atoms such as oxygen, sulfur, nitrogen, and the substituent can be C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 1 -C 4 Alkylmercapto, C 1 -C 4 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C 1 -C 4 Alkoxyacyl, C 1 -C 4 An acyloxy group;
R 2 the substituent group in any position shown in the general formula (I) or (II) can be monosubstituted, disubstituted or trisubstituted of the same or different groups;
R 2 selected from hydrogen, C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 1 -C 4 Alkylmercapto, C 1 -C 4 Alkylamino, C 1 -C 4 Alkoxyacyl, C 1 -C 4 Acyloxy, halogeno C 1 -C 4 Alkyl, halo C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkylmercapto, halo C 1 -C 4 Alkylamino, halo C 1 -C 4 Alkoxyacyl, halo C 1 -C 4 Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide or aryl containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more hetero atoms such as oxygen, sulfur, nitrogen, and the substituent can be C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 1 -C 4 Alkylmercapto, C 1 -C 4 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C 1 -C 4 Alkoxyacyl, C 1 -C 4 An acyloxy group.
Still further preferred technical solutions of the present invention are: in the general formula (I) or (II)
X is C; y is C;
R 1 selected from hydrogen, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, dibromomethyl, tribromomethyl, C 1 -C 6 Alkyl, halo C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl, halo C 3 -C 6 Cycloalkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, halo C 2 -C 6 Alkenyl, halo C 2 -C 6 Alkynyl, C 1 -C 6 Ester group, C 1 -C 6 Acetoxy group, C 1 -C 6 Cyano, either phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more hetero atoms such as oxygen, sulfur, nitrogen, and the substituent can be C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 1 -C 4 Alkylmercapto, C 1 -C 4 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C 1 -C 4 Alkoxyacyl, C 1 -C 4 An acyloxy group;
R 2 the substituent group in any position shown in the general formula (I) or (II) can be monosubstituted, disubstituted or trisubstituted of the same or different groups;
R 2 selected from hydrogen, C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 1 -C 4 Alkylmercapto, C 1 -C 4 Alkylamino, C 1 -C 4 Alkoxyacyl, C 1 -C 4 Acyloxy, halogeno C 1 -C 4 Alkyl, halo C 1 -C 4 Alkoxy, halo C 1 -C 4 Alkylmercapto, halo C 1 -C 4 Alkylamino, halo C 1 -C 4 Alkoxyacyl, halo C 1 -C 4 Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide or aryl containing one or more substituents,
aryl groups may be phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other hetero-containing one or more hetero-atoms such as oxygen, sulfur, nitrogen, and the likeAryl, substituent may be C 1 -C 4 Alkyl, C of (2) 1 -C 4 Alkoxy, C 1 -C 4 Alkylmercapto, C 1 -C 4 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C 1 -C 4 Alkoxyacyl, C 1 -C 4 An acyloxy group.
The invention also provides salts of the compounds represented by the general formula (I) or (II) with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid, citric acid or the like.
In the definition of compounds (I) or (II) given above, the terms used in the collection generally represent the following substituents:
halogen: refers to fluorine, chlorine, bromine or iodine. Alkyl: linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl or tert-butyl. Cycloalkyl: a substituted or unsubstituted cyclic alkyl group such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen, and the like. Haloalkyl: linear or branched alkyl groups, the hydrogen atoms on these alkyl groups may be partially or fully substituted with halogen atoms, for example: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like. An alkoxy group: a linear or branched alkyl group linked to the structure via an oxygen atom bond. Haloalkoxy: straight-chain or branched alkoxy groups, the hydrogen atoms on these alkoxy groups may be partially or completely substituted with halogen atoms. For example: chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like. Alkylthio: a linear or branched alkyl group linked to the structure via a sulfur atom linkage. Haloalkylthio: linear or branched alkylthio groups, the hydrogen atoms on these alkyl groups may be partially or fully substituted by halogen atoms, for example: chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like. Alkenyl: straight or branched chainAlkenes such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Alkenyl groups also include polyenes such as 1, 2-allenyl and 2, 4-hexadienyl. Haloalkenyl: straight-chain or branched-chain olefins, the hydrogen atoms on these alkenyl groups may be partially or completely substituted with halogen atoms. Alkynyl: straight or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. Alkynyl also includes groups consisting of multiple triple bonds, such as 2, 5-hexadiynyl. Haloalkynyl: straight-chain or branched alkynes in which the hydrogen atoms on the alkynyl groups may be partially or fully replaced by halogen atoms. Alkenyloxy: linear or branched alkenes are linked to the structure via oxygen atom bonds. Haloalkenyloxy: straight-chain or branched alkenyloxy groups, the hydrogen atoms on these alkenyloxy groups may be partially or completely substituted with halogen atoms. Alkynyloxy: straight or branched alkynes are linked to the structure via an oxygen atom bond. Halogenated alkynyloxy: straight-chain or branched alkynyloxy groups, the hydrogen atoms on these alkynyloxy groups may be partially or entirely substituted with halogen atoms. Alkenyloxycarbonyl: such as CH 2 ＝CHCH 2 OCO-, and the like. Alkynyloxycarbonyl: such as CH≡CCH 2 OCO-, and the like. Alkylamino: a linear or branched alkyl group linked to the structure via a nitrogen atom bond.
Haloalkyl amino: straight-chain or branched alkylamino groups, the hydrogen atoms on these alkyl groups may be partially or fully substituted with halogen atoms. Dialkylamino group: for example (CH) 3 ) 2 NH-，(C 2 H 5 ) 2 NH-. Alkylsulfinyl group: the linear or branched alkyl group is attached to the structure via a sulfinyl (-SO-) group, such as methylsulfinyl. Cyanoalkoxy groups: CN-alkoxy, e.g. CNCH 3 O，CNC 2 H 5 O. Alkylsulfinyl group: the linear or branched alkyl group is attached to the structure via a sulfinyl (-SO-) group, such as methylsulfinyl. Haloalkyl sulfinyl: straight-chain or branched alkylsulfinyl groups in which hydrogen atoms on the alkyl groups may be partially or completely replaced with halogen atoms. Alkylsulfonyl: straight or branched chain alkyl is sulfonyl (-SO) 2 (-) is attached to a structure such as methylsulfonyl. Haloalkylsulfonyl: straight-chain or branched alkylsulfonyl, its alkaneThe hydrogen atoms on the radicals may be partially or fully substituted by halogen atoms. Alkylcarbonyl: the alkyl groups being bound to the structure by carbonyl groups, e.g. CH 3 CO-，CH 3 CH2CO-. Haloalkylcarbonyl: the hydrogen atoms on the alkyl groups of the alkylcarbonyl groups may be partly or wholly substituted by halogen atoms, e.g. CF 3 CO-. Alkoxycarbonyl: alkyl-O-CO-, such as CH3OCO-, C 2 H 5 OCO-. Haloalkoxycarbonyl: the hydrogen atoms on the alkyl groups of the alkoxycarbonyl groups being partly or wholly substituted by halogen atoms, e.g. ClCH 2 CH 2 OCO-、CF 3 CH 2 OCO-, and the like. Alkoxycarbonylalkyl: alkoxycarbonyl-alkyl-, e.g. CH 3 OCOCH 2 -. Alkoxyalkyl groups: alkyl-O-alkyl-, e.g. CH 3 OCH 2 -. Haloalkoxyalkyl: the hydrogen atoms on the alkyl groups of the alkoxyalkyl groups may be partially or completely substituted with halogen atoms. Such as ClCH 2 CH 2 OCH 2 -. Alkylthio alkyl: alkyl-S-alkyl-, e.g. CH 3 SCH 2 -. Haloalkylthioalkyl: the hydrogen atoms of the alkyl groups of the alkylthio-alkyl groups being partly or wholly substituted by halogen atoms, e.g. ClCH 2 CH 2 SCH 2 -、CF 3 CH 2 SCH 2 -and the like. Alkyl sulfamoyl: alkyl-NH-SO 2 -. Cycloalkyl-oxy carbonyl: such as cyclopropoxycarbonyl, cyclohexyloxycarbonyl, and the like. Alkyl carbonyl alkyl: alkyl-CO-alkyl-. Alkylaminocarbonyl group: alkyl-NH-CO-, for example: CH (CH) 3 NHCO-、(CH 3 ) 2 NCO-. Dialkylaminocarbonyl groups: (alkyl) 2 -NH-CO-, for example: (CH) 3 ) 2 -N-CO-、(C 2 H 5 ) 2 -N-CO-. An alkoxycarbonyl group: such as CH 3 OCH 2 CH 2 OCO-, and the like. Alkyl amino carbonyl alkyl: for example CH 3 NH 2 COCH 2 -. Dialkylaminocarbonylalkyl: for example (CH) 3 ) 2 NH 2 COCH 2 -. Aryl: including phenyl or naphthyl, and the like. Heteroaryl group: refers to five-membered or six-membered rings containing 1 or more N, O, S heteroatoms. For example: pyrrolyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, and isoxazolylThiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyridazinonyl, indolyl, benzofuranyl, benzoxazolyl, benzothienyl, benzothiazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, benzopyrazolyl, quinoxalinyl and the like. Aryloxy group: including phenoxy, and the like. Heteroaryloxy: including pyridyloxy and the like. (hetero) arylcarbonyl: such as benzoyl, 4-chlorobenzoyl, picolyl, pyrimidinyl, pyrazinyl and the like. (hetero) aryloxycarbonyl: such as phenoxycarbonyl, 4-chlorophenoxycarbonyl, 4-nitrophenoxycarbonyl, naphthyloxycarbonyl, pyridyloxycarbonyl, pyrimidinyloxycarbonyl, and the like. (hetero) arylcarbonylalkyl: such as PhCOCH 2 -. (hetero) aryloxycarbonylalkyl: such as PhOCOCH 2 -. (hetero) arylalkyl: such as benzyl, phenethyl p-chlorophenyl methyl group,Etc. Aryloxyalkyl groups such as:etc. Glycosyl: refers to an alcohol glycosyl or an aldehyde glycosyl, such as a glycosyl, a galactosyl and the like. Amino acid: refers to organic compounds containing amino and carboxyl groups, such as glutamic acid, cysteine, lysine, proline, valine, arginine, tryptophan, leucine, and the like. Peptide chain: refers to chain or cyclic oligopeptides and polypeptides formed by dehydration condensation of identical or different amino acids.
The term "acceptable salt" refers to salts whose cations or anions are known and which can be used in the art to form a use.
Suitable salts having bases, for example: salts formed from compounds of formula (I) or (II) containing a carboxyl group include salts of alkali metals (e.g., sodium and potassium), alkaline earth metals (e.g., calcium and magnesium), ammonium and amines.
Suitable salts with acid groups, such as those formed from compounds of formula (I) or (II) containing an amino group, include salts with inorganic acids, for example, hydrochloride, sulfate, sulfite, phosphate, hydrogen phosphate and nitrate, and salts with organic acids such as acetic acid, malic acid, tartaric acid, citric acid, lactic acid, salicylic acid and oxalic acid.
Some of the compounds of the present invention are exemplified by the specific compounds listed below, but the present invention is not limited to these compounds.
The reaction path of the compound of the general formula (I) or (II) is shown as the formulas (1) and (2), wherein X 1 Is Cl or Br or I.
The preparation method of the compounds I-1 to I-37 is shown in a reaction path (1); the preparation method of the compounds II-1 to II-37 is shown in a reaction path (2).
(1)
(2)
X in the formula 1 Refers to chlorine, bromine or iodine.
The alkali refers to potassium carbonate or potassium tert-butoxide.
The compounds of the present invention are useful for controlling and destroying a wide range of agricultural and forestry pests, hygiene pests and pests that are harmful to animal health. In the present specification, the "insecticide" is a generic term for a substance having an effect of controlling all the pests mentioned above. Examples of pests include, but are not limited to: lepidoptera (Lepidoptera) insects: for example, plutella xylostella (Plutella xylostella), spodoptera frugiperda (Spodoptera frugiperda), spodoptera exigua (s. Exigua), spodoptera litura (s. Litura), gypsylla (Lymantria dispar), trichostrongylus, chrysalis (Malacosoma neustria testacea), cotton bollworm (Diaphania perspectalis), armyworm (Clania variegata), yellow thorn (Cnidocampa flauescens), pine moth (Dendrolimus punctatus), archaea (Orgyia antipquata), white poplar diatom moth (Paranthrene tabaniformis), chilo suppressalis (Chilo suppressalis), corn borer (Ostrinia nubilalis), pink bollworm (Ephestia cautella), cotton bollworm (adophis orana), chestnut plutella (laspyresia splendana), tiger (Agrotis fucosa), large wax moth (Galleria mellonella), citrus moth (Phyllocnistis citrella), oriental myxoma (Mythimna separata), and the like; coleopteran (Coleoptera) insects: for example, corn weevil (Sitophilus zeamais), red larch (Tribolium castaneum), potato ladybug (Henosepilachna vigintioctomaculata), eicosmosa (h.sparsa), fine chest click beetle (Agriotes fusciollis), red foot mossback (Anomala cuprapes), red foot beetle (Popillia quadriguttata), potato leaf beetle (Monolepta hieroglyphica), monochamus alternatus (Monochamus alternatus), rice root weevil (Echinocnemus squameus), paulownia leaf beetle (Basiprionota bisignata), star beetle (Anoplophora chinensis), mulberry beetle (Apripona germari), umbilical bark beetle (socytus scheve), or fine chest flammule (Agriotes fuscicollis), etc.; hemiptera (Hemiptera) insects: for example, lygus lucorum (Stephanitis nashi), lygus lucorum (Nezara viridula), theragra chalcogramma (Poecilocoris latus), theragra chalcogramma (Cletus pubtiger), lygus sorghum halepense (Dimorphopterus japonicus), lygus lucorum (Dysdercus cingulatus), etc.; homoptera (Homoptera) insects: for example, leafhoppers (Nephotettix cincticeps), cerclage (Unaspis yanonensis), myzus persicae (Myzus persicae), cotton aphid (Aphis gossypdii), bemisia tabaci (Bemisia tabaci), brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), white-back planthopper (Sogatella furcifera), and the like; orthoptera (Orthoptera) insects: for example, mole cricket africa (Gryllotalpa africana), locusta migratoria (locusta migratoria), etc.; hymenoptera (Hymenoptera) insects: for example, solenopsis invicta (Solenopsis invicta), apis cerana (Tremex fuscicornis), etc.; insects of the order blattaria: for example, german cockroaches (Blattella germanica), american cockroaches (Periplaneta american), coptotermes (Copotermes formosamus), and the like; diptera (Diptera) insects: for example, house flies (Musca domestica), aedes aegypti (Aedes aegypti), seed flies (Delia platura), culex (Culex fatigans), anopheles sinensis (Anopheles sinensis), and the like; plant parasitic nematodes: such as root-knot nematodes, root-rot nematodes, aphelenchus xylophilus, pine nematodes, etc. Pests that are harmful to animal health include tick (Boophilus microplus) of nigella minutissima, tick (Haemaphysalis longicornis) of rhizus, tick (Hyalomma anatolicum) of rhizus, cow fly (Hypoderma bovis), fasciola hepatica (Fasciola hepatica), taenia bellifer (Moniezia blanchard), protozoa (Trypanosoma enansi), barbus Bei Sichong (Babesia bigemina), and the like.
The compounds of the general formula (I) or (II) show a controlling effect on pests in the technical field of agriculture. Thus, a further embodiment of the invention relates to the use of the compounds of the general formula (I) or (II) as pesticides, i.e. the use of the compounds of the general formula (I) or (II) for producing pesticides in agriculture or in other fields.
In particular, the preferred compounds of formula (I) or (II) exhibit a good poisoning effect against chewing pests such as plutella xylostella, spodoptera frugiperda, spodoptera exigua, and spodoptera litura.
An insecticidal composition comprising an active ingredient (a compound of formula (I) or (II)) and an agriculturally acceptable carrier, the weight percentage of the active ingredient in the composition being from 0.01 to 99.99%;
a process for the preparation of a composition as defined above: the compounds of the general formula (I) or (II) are mixed with a carrier. The active ingredient in such a composition may comprise a single compound of the invention or a mixture of several compounds.
The above composition may be applied in the form of a formulation. The compounds of the general formula (I) or (II) are dissolved or dispersed as active ingredients in a carrier or formulated so as to be more readily dispersible for use as pesticides. For example: the chemical preparation can be prepared into powder, wettable powder, emulsifiable concentrate, concentrated emulsion and microemulsion, suspension emulsion, granule, oil agent, ultra-low volume spray, smoke type, slow release agent and other pesticide formulations. In these compositions, at least one liquid or solid carrier is added, and a suitable surfactant may be added as needed.
The carrier in the composition of the invention is a substance that satisfies the following conditions: it is formulated with the active ingredient for ease of application to the locus to be treated, for example, it may be a plant, seed or soil; or to facilitate storage, transport or handling. The carrier may be a solid or a liquid, including substances that are normally gaseous but which have been compressed into a liquid, and commonly used in formulating insecticidal compositions.
The agricultural composition can be used for killing or preventing agricultural and forestry pests, sanitary pests or pest pesticides which harm animal health.
The use according to the preceding claim, wherein the insecticide is applied to the pest or to the medium on which the pest is growing.
For certain applications, such as agriculture, one or more other types of insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers, etc., may be added to the insecticide compositions of the present invention, thereby producing additional advantages and effects.
It should be understood that various changes and modifications can be made within the scope of the invention as defined in the appended claims.
Compared with the prior art, the invention has the following advantages:
the compound of the general formula (I) or (II) has insecticidal activity on pests in agriculture, forestry and other fields, and meanwhile, the compound of the general formula (I) or (II) is used as an insecticide, namely, the compound of the general formula (I) or (II) is used for preparing medicines for controlling the pests in agriculture, forestry or other fields. In particular to the lepidoptera pests such as plutella xylostella, spodoptera litura, asparagus caterpillar and the like.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market. For process parameters not specifically noted, reference may be made to conventional techniques.
Synthesis example 1: preparation of Compound I-10
Step one: benzimidazole (0.40 mmol), K, was added to the sealed tube 2 CO 3 (0.80 mmol) and dissolved with 2mL of acetonitrile (MeCN), followed by addition of 3-bromo-2-butanone (0.60 mmol), and the reaction tube was sealed and placed in an oil bath at 80℃and stirred for reaction for 8h. After TLC monitoring the reaction, after the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, the organic phases were combined, and taken over anhydrous Na 2 SO 4 After drying, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a yellow oil in 67.8% yield.
Step two: to the sealed tube was added the product of step one (0.20 mmol), selenium powder (0.40 mmol), potassium tert-butoxide (KTB) (0.40 mmol), and dissolved with 2mL acetonitrile (MeCN), followed by ethyl bromofluoroacetate (0.50 mmol), and the reaction tube was sealed and placed in an oil bath at 100℃under stirring for 24 hours. After TLC monitoring the reaction, after the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, the organic phases were combined over anhydrous Na 2 SO 4 After drying, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a colorless oil in 42.7% yield.
The compounds I-1 to I-37 are prepared by a method of referencing the compound I-10.
Synthesis example 2: preparation of Compound II-5
1-Isopropylimidazole (0.20 mmol), selenium powder (0.40 mmol), potassium tert-butoxide (KTB) (0.40 mmol) and dissolved in 2mL acetonitrile (MeCN) were added to the sealed tube followed by ethyl bromofluoroacetate (0.50 mmol)) The reaction tube was sealed and placed in a 100 ℃ oil bath with stirring for reaction for 24 hours. After TLC monitoring the reaction, after the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, the organic phases were combined over anhydrous Na 2 SO 4 After drying, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a brown liquid product in 60.0% yield.
Preparation of compounds II-1 to II-37 by reference to compound II-5
Nuclear magnetic data of some compounds (other compounds, except for the special notes: 1 H NMR,500MHz； 13 c NMR,125MHz, internal standard TMS, solvent: CDCl 3 ) The following are provided:
compound I-1: a pink solid. 13 H NMR(500MHz,CD 3 COCD 3 ):δ H 8.27(t,J＝58.38Hz,1H),7.64(m,2H),7.43(dtd,J＝1.13,7.60,21.79,2H),4.49(m,1H),1.79(m,1H),1.73(m,2H),1.04(m,1H),1.02(m,1H)； 13 C NMR(125MHz,CD 3 COCD 3 ):δ C 166.99(t,J C-F ＝3.62Hz,1C),133.67,129.47,125.59,124.87,113.36(t,J C-F ＝248.23Hz,1C),111.80(t,J C-F ＝2.88Hz,1C),111.26,45.23,36.44,26.43,22.42(2C).
Compound I-2: a pink solid. Delta H 8.18(t,J＝58.48Hz,1H),7.60(d,J＝7.50Hz,1H),7.24–7.33(m,3H),5.27(t,J＝6.67Hz,1H),5.07(d,J＝6.66Hz,1H)；δ C 166.22(t,J C-F ＝3.60Hz,1C),137.89,132.98,129.23,124.74,124.19,116.90,112.51(t,J C-F ＝250.16Hz,1C),111.63(t,J C-F ＝2.71Hz,1C),110.22,45.02,25.55,18.57.
Compound I-3: as a yellow oil. Delta H 8.16(t,J＝58.45Hz,1H),7.61(d,J＝7.63Hz,1H),7.38–7.27(m,3H),5.86(ddt,J＝17.07,10.19,6.87Hz,1H),5.21–4.97(m,2H),4.58–4.32(m,2H),2.63(dd,J＝14.77,7.27Hz,2H)；δ C 166.32(t,J＝3.68Hz,1C),133.44,133.05,129.05,124.77,124.21,118.10,112.33(t,J C-F ＝250.18Hz,1C),111.66(t,J C-F ＝2.73Hz,1C),110.70,109.92,45.77,31.69.
Compound I-4: light weightA pink solid. Delta H 8.17(t,J＝58.47Hz,1H),7.61(d,J＝7.74Hz,1H),7.40–7.22(m,3H),5.85(ddt,J＝16.78,10.18,6.48Hz,1H),5.14–4.98(m,2H),4.44–4.33(m,2H),2.22(q,J＝7.07Hz,2H),2.02–1.90(m,2H)；δ C 166.27(t,J C-F ＝3.42Hz,1C),136.74,133.02,129.11,124.76,124.20,115.81,111.67(t,J C-F ＝2.61Hz,1C),112.36(t,J C-F ＝250.16Hz,1C),109.79,45.82,30.67,26.42.
Compound I-5: pale yellow solid. Delta H 8.17(t,J＝58.49Hz,1H),7.61(d,J＝7.63Hz,1H),7.32(m,3H),5.79(m,1H),5.01(m,2H),4.39(m,2H),2.15(q,J＝7.13Hz,2H),1.89(m,2H),1.56(m,2H)；δ C 166.33(t,J＝3.65Hz,1C),137.87,133.08,129.17,124.78,124.20,115.14,114.40,112.41,111.73,111.71,111.69,110.42,109.83,77.25,77.00,76.75,46.27,40.99,33.15,27.36,26.94,25.94,25.89.
Compound I-6: as a yellow oil. Delta H 8.18(t,J＝58.49Hz,1H),7.61(d,J＝7.69Hz,1H),7.37–7.27(m,3H),4.44–4.31(m,2H),1.85(dt,J＝15.43,7.64Hz,2H),1.46–1.18(m,11H),0.87(d,J＝13.84Hz,3H)；δ C 166.20(t,J＝3.51Hz,1C),133.08,129.13,124.73,124.14,113.39(d,J C-F ＝251.13Hz,1C),111.65(d,J C-F ＝2.63Hz,1C),109.84,46.46,31.66,29.09,29.01,27.50,26.75,22.51,13.97.
Compound I-7: a pale pink solid. 13 H NMR(500MHz,CD 3 COCD 3 ):δ H 8.30(t,J＝58.34Hz,1H),7.69(dd,J＝9.95,3.90Hz,2H),7.47–7.38(m,4H),7.31(t,J＝7.46Hz,2H),7.27–7.22(m,1H),6.85(d,J＝15.97Hz,1H),6.44(dt,J＝15.96,6.21Hz,1H),5.33(dd,J＝6.2,1.3Hz,2H)； 13 C NMR(125MHz,CD 3 COCD 3 ):δ C 167.65(t,J C-F ＝3.85Hz,1C),136.75,134.75,133.78,129.55,129.14,128.55,127.07,125.65,124.99,122.28,113.48(t,J C-F ＝248.38Hz,1C),111.85(t,J C-F ＝2.89Hz,1C),111.72,48.60.
Compound I-8: a pink solid. Delta H 8.14(t,J＝58.38Hz,1H),7.61(d,J＝7.95Hz,1H),7.45(d,J＝7.89Hz,1H),7.34(dt,J＝15.38,8.01Hz,2H),4.66(t,J＝7.05Hz,2H),3.67(s,3H),2.99(t,J＝7.05Hz,2H)；δ C 171.20,166.52(t,J＝3.68Hz,1C),132.99,129.06,124.91,124.41,112.22(t,J C-F ＝250.38Hz,1C),111.66(t,J C-F ＝2.76Hz,1C),110.30,52.04,42.01,31.91.
Compound I-9: a pink solid. Delta H 8.14(t,J＝58.38Hz,1H),7.62(d,J＝7.70Hz,1H),7.39–7.29(m,2H),7.17(d,J＝8.61Hz,1H),5.08(s,2H),1.47(s,9H)；δ C 168.41(t,J C-F ＝3.81Hz,1C),164.90,133.16,128.97,125.03,124.46,112.43(t,J C-F ＝250.56Hz,1C),111.81(t,J C-F ＝2.73Hz,1C),109.69,83.58,47.88,27.95.
Compound I-10: colorless oily. Delta H 8.17(t,J＝58.29Hz,1H),7.65(d,J＝7.69Hz,1H),7.38–7.26(m,2H),7.10(d,J＝7.82Hz,1H),6.26(dd,J＝13.99,6.91Hz,1H),2.08(s,3H),1.65(d,J＝7.20Hz,3H)；203.15,168.13,131.20,129.36,125.13,124.64,112.76(t,J C-F ＝251.29Hz,1C),112.10(t,J C-F ＝2.81Hz,1C),110.77,62.56,27.15,12.77.
Compound I-11: a pale pink solid. Delta H 8.09(t,J＝58.26Hz,1H),7.63(d,J＝7.84Hz,1H),7.49–7.30(m,3H),4.65(t,J＝6.71Hz,2H),3.05(t,J＝6.70Hz,2H)；δ C 166.68(t,J＝3.50Hz,1C),132.57,128.90,125.24,124.82,116.87,111.99(t,J C-F ＝250.92Hz,1C),111.86(t,J C-F ＝2.77Hz,1C),109.72,41.92,16.24.
Compound I-12: yellow solid. Delta H 8.13(t,J＝58.37Hz,1H),7.62(t,J＝7.58Hz,1H),7.40-7.31(m,3H),4.80(m,2H),3.51(m,2H)；δ C 166.53(t,J C-F ＝3.62Hz,1C),132.93,129.15,125.10,124.57,113.28(t,J C-F ＝250.76Hz,1C),111.90(t,J C-F ＝2.58Hz,1C),109.75,46.89(d,J C-F ＝79.10Hz,1C),25.67(d,J C-F ＝269.12Hz,1C).
Compound I-13: pale yellow solid. Delta H 8.21(t,J＝58.40Hz,1H),7.73(d,J＝7.59Hz,1H),7.63(d,J＝7.94Hz,1H),7.39–7.27(m,2H),6.06(m,J＝9.19Hz,1H),3.05–2.85(m,2H),2.65–2.44(m,2H),2.15–1.92(m,2H)；δ C 166.29(t,J＝3.48Hz,1C),132.27,129.62,124.35,124.05,112.74(t,J C-F ＝250.71Hz,1C),111.97(t,J C-F ＝2.95Hz,1C),111.24,52.41,27.36,14.56.
Compound I-14: yellow solid. Delta H 8.19(t,J＝58.48Hz,1H),7.60(d,J＝8.13Hz,1H),7.35–7.28(m,3H),4.21(d,J＝7.44Hz,2H),2.15(m,1H),1.69(m,5H),1.18(m,5H)；δ C 166.80(t,J＝3.50Hz,1C),133.78,128.98,124.63,124.07,112.47(t,J C-F ＝250.18Hz,1C),111.56(t,J C-F ＝2.68Hz,1C),110.29,52.43,36.76,30.88,30.71,26.03,25.54.
Compound I-15: pale yellow solid. Delta H 8.17(t,J＝58.40Hz,1H),7.60(d,J＝7.73Hz,1H),7.47(d,J＝7.81Hz,1H),7.39–7.27(m,2H),5.34(t,J＝4.32Hz,1H),4.62(d,J＝4.34Hz,2H),4.04–3.97(m,2H),3.93–3.87(m,2H)；δ C 167.77(t,J＝3.72Hz,1C),133.73,128.96,124.80,124.32,112.48(t,J C-F ＝250.43Hz,1C),111.43(t,J C-F ＝2.72Hz,1C),111.16,100.96,65.19(2C),48.86.
Compound I-16: white solid. Delta H 8.20(t,J＝58.3Hz,1H),7.81(d,J＝14.1Hz,1H),7.70(d,J＝8.1Hz,1H),7.42–7.33(m,1H),7.33–7.20(m,3H),6.85(d,J＝8.0Hz,1H)δ C 168.11(t,J＝3.73Hz,1C),162.02(d,J CF ＝251.34Hz,1C),135.61(d,J C-F ＝10.19Hz,1C),135.24(d,J C-F ＝8.59Hz,1C),133.39,129.08,125.28,124.88,119.30(d,J C-F ＝22.14Hz,1C),118.67(d,J C-F ＝24.41Hz,1C),117.51(d,J C-F ＝4.04Hz,1C),112.33(t,J C-F ＝251.13Hz,1C),111.78(t,J C-F ＝2.68Hz,1C),110.45.
Compound I-17: a tan solid. Delta H 8.14(t,J＝58.32Hz,1H),7.69–7.59(m,1H),7.38–7.28(m,2H),7.26–7.18(m,1H),5.71(s,2H)；δ C 168.05(t,J C-F ＝3.71Hz,1C),146.41(ddt,J C-F ＝3.89,7.79,11.69Hz,1C),144.42(ddt,J C-F ＝3.95,7.93,11.85Hz,1C),140.69(m,1C),138.62(ddd,J C-F ＝2.54,10.16,18.48Hz,1C),132.64,129.03,125.10,124.68,112.37(t,J C-F ＝250.95Hz,1C),111.91(t,J C-F ＝2.74Hz,1C),109.62,107.80(td,J C-F ＝3.98,16.13Hz,1C),39.04.
Compound I-18: a pale pink solid. Delta H 8.11(t,J＝58.27Hz,1H),7.72(s,1H),7.64(d,J＝8.95Hz,1H),7.42–7.30(m,3H),5.72(s,2H)；δ C 153.53,141.44,133.04,132.11,129.30,125.27,124.91,113.32(t,J C-F ＝251.04Hz,1C),112.33,112.19(t,J C-F ＝2.70Hz,1C),109.52,99.95,42.29.
Compound I-19: white solid. Delta H 8.21(t,J＝58.38Hz,1H),7.63(dd,J＝18.71,8.06Hz,1H),7.43(d,J＝8.58Hz,2H),7.30(m,2H),7.20–7.16(m,3H),5.67(s,2H)；δ C 167.95,149.08,132.94,132.88,129.34,129.14(2C),125.08,124.63,121.39,112.64,111.93,110.30,49.11.
Compound I-20: a pale pink solid. Delta H 8.23(t,J＝58.45Hz,1H),7.62(d,J＝7.91Hz,1H),7.30-7.18(5H),7.14(d,J＝7.14Hz,2H),5.63(s,2H),2.31(s,3H)；δ C 167.69(t,J＝3.94Hz,1C),138.07,133.10,131.26,129.58,127.58,124.89,124.36,112.72(t,J C-F ＝250.46Hz,1C),111.73(t,J C-F ＝2.65Hz,1C),110.65,49.81,21.11.
Compound I-21: white solid. Delta H 8.25(t,J＝58.44Hz,1H),7.65(d,J＝7.85Hz,1H),7.55(d,J＝8.44Hz,4H),7.44(m,4H),7.36-7.22(m,4H),5.72(s,2H)；δ C 167.85(t,J＝3.46Hz,1C),141.24,140.38,133.22,133.09,129.36,128.79,128.01,127.64,127.50,127.03,124.98,124.47,112.71(t,J C-F ＝250.46Hz,1C),111.81(t,J C-F ＝2.61Hz,1C),110.62,49.71.
Compound I-22: yellow solid. 13 H NMR(500MHz,CD 3 COCD 3 ):δ H 8.49–8.20(m,3H),7.89(d,J＝8.81Hz,1H),7.51(d,J＝7.46Hz,2H),7.35(dt,J＝26.15,7.20Hz,3H),5.89(s,2H)； 13 C NMR(125MHz,CD 3 COCD 3 ):δ C 172.05(t,J C-F ＝3.40Hz,1C),145.85,135.11,129.45(2C),128.77,128.26(2C),120.97,113.38(t,J C-F ＝250.73Hz,1C),111.97(t,J C-F ＝3.38Hz,1C),107.23,50.07.
Compound I-23: yellow solid. Delta H 8.48(s,1H),8.19(d,J＝58.23Hz,1H),8.19(dd,J＝8.82,2.10Hz,1H),7.38–7.32(m,5H),7.22(d,J＝8.90Hz,1H),5.70(s,2H):δ C 172.01(t,J C-F ＝3.42Hz,1C),144.47,137.16,133.36,129.22(2C),129.16,128.74,127.52(2C),121.18,113.35(t,J C-F ＝252.62Hz,1C),110.04,107.42(t,J C-F ＝3.11Hz,1C),50.29.
Compound I-24: a pink solid. Delta H 8.16(t,J＝58.33Hz,1H),7.50–7.42(m,1H),7.40–7.31(m,5H),6.96(dd,J＝9.04,6.57Hz,1H),5.62(s,2H)；δ C 169.24,149.43(dd,J C-F ＝14.38,63.44Hz,1C),147.46(dd,J C-F ＝14.38,63.44Hz,1C),133.51,129.15(2C),129.10,128.61,127.50(2C),127.41,112.40(t,J C-F ＝251.50Hz,1C),101.19(d,J C-F ＝24.34Hz,1C),99.79(d,J C-F ＝23.78Hz,1C),50.26.
Compound I-25: a pale pink solid. Delta H 8.16(t,J＝58.45Hz,1H),7.18(dd,J＝30.19,39.04Hz,2H),6.94(d,J＝2.33,8.85Hz,1H),3.87(s,3H),3.84(s,3H)；δ C 165.77,157.56,129.80,127.88,112.62,112.42(t,J C-F ＝250.25Hz,1C),110.25,96.70(t,J C-F ＝2.75Hz,1C),56.03,32.99.
Compound I-26: a pale pink solid. Delta H 8.13(t,J＝58.58Hz,1H),7.38(s,1H),7.05(s,1H),3.83(s,3H),2.35(d,J＝6.40Hz,6H)；δ C 165.53,134.05,133.58,132.01,127.28,112.40(t,J C-F ＝249.53Hz,1C),112.26(t,J C-F ＝2.53Hz,1C),110.35,32.88,20.26,20.14.
Compound I-27: a pale pink solid. Delta H 8.11(t,J＝58.36Hz,1H),7.50–7.38(m,3H),3.84(s,3H)；δ C 168.22(t,J C-F ＝3.33Hz,1C),134.84,128.12,127.37,118.38,112.93,112.65(t,J C-F ＝2.88Hz,1C),112.25(t,J C-F ＝250.93Hz,1C),32.99.
Compound I-28 (XLT-52): brick red solid. Delta H 8.19(t,J＝58.55Hz,1H),7.40(s,1H),7.28(s,1H),5.79(m,1H),2.36(s,3H),2.34(s,3H),1.60(d,J＝7.05Hz,6H).δ C ＝164.29,133.34,133.19,129.80,128.15,112.83(t,J C-F ＝250.26Hz,1C),112.43(t,J C-F ＝2.77Hz,1C),112.09,51.40,20.39,20.04,19.66(2C).
Compound I-29: yellow solid. Delta H 8.41(s,1H),8.23(dd,J＝9.01,1.68Hz,1H),8.14(t,J＝58.55Hz,1H),7.62(d,J＝9.02Hz,1H),5.80(m,1H),1.62(d,J＝7.22Hz,6H).δ C ＝170.10,143.75,135.65,129.45,120.38,112.30(t,J C-F ＝252.42Hz,1C),110.66,107.12(t,J C-F ＝3.20Hz,1C),51.82,19.45(2C).
Compound I-30: yellow solid. Delta H 8.36(d,J＝1.94Hz,1H),8.22(dd,J＝8.92,2.03Hz,1H),8.16(t,J＝58.39Hz,1H),7.70(d,J＝8.91Hz,1H),5.78(m,1H),1.65(d,J＝7.18Hz,6H).δ C ＝169.53,144.37,133.69,131.44,119.76,112.28(t,J C-F ＝252.47Hz,1C),111.14(t,J C-F ＝3.14Hz,1C),106.59,51.90,19.43(2C).
Compound I-31: white solid. Delta H 8.17(t,J＝58.33Hz,1H),7.65(d,J＝1.55Hz,1H),7.49(d,J＝8.62Hz,1H),7.42(dd,J＝8.63,1.67Hz,1H),5.79(m,1H),1.60(d,J＝7.14Hz,6H).δ C ＝167.02,132.63,128.83,126.95,117.79,114.30,112.78(t,J C-F ＝2.97Hz,1C),112.63(t,J C-F ＝251.52Hz,1C),51.62,19.58(2C).
Compound I-32: white solid. Delta H 8.17(t,J＝58.33Hz,1H),7.77(s,1H),7.43(dd,J＝8.71,1.71Hz,1H),7.37(d,J＝8.7Hz,1H),5.79(m,1H),1.59(d,J＝7.11Hz,6H).δ C ＝166.65,130.78,130.60,127.44,117.45,114.93(t,J C-F ＝3.22Hz,1C),112.58(t,J C-F ＝250.87Hz,1C),112.29,51.66,19.62(2C).
Compound I-33: yellow solid. Delta H 8.18(t,J＝58.39Hz,1H),7.55(dt,J＝15.41,7.70Hz,1H),7.24(dd,J＝8.66,2.21Hz,1H),7.05(td,J＝9.00,2.30Hz,1H),5.81(m,1H),1.60(d,J＝7.14Hz,6H)；δ C 167.30,159.86(d,J＝243.74Hz),132.02(d,J＝12.21Hz),112.73(d,J＝250.87Hz),112.45(dt,J＝9.83,3.11Hz),111.38(d,J＝24.85Hz),99.24(d,J＝28.94Hz),51.58,19.49(2C).
Compound I-34: yellow solid. Delta H 8.19(t,J＝58.34Hz,1H),7.45(dd,J＝8.98,4.26Hz,1H),7.36(m,1H),7.06(td,J＝9.00,2.48Hz,1H),5.80(m,1H),1.61(d,J＝7.12Hz,6H)；δ C 166.61,159.70(d,J＝244.61Hz),130.32(d,J＝12.7Hz),127.95,112.63(d,J＝251.2Hz),112.02(2C),111.87(d,J＝13.37Hz),99.90(dt,J＝28.89,3.09Hz),51.67,19.67(2C).
Compound I-35: yellow brown solid. Delta H 8.16(t,J＝58.45Hz,1H),7.69(s,1H),7.58(s,1H),5.75(m,1H),1.59(d,J＝7.14Hz,6H).δ C ＝167.86,130.75,128.87,128.49,114.39,112.91(t,J C-F ＝3.26Hz,1C),112.39(t,J C-F ＝251.73Hz,1C),112.33,51.65,19.51(2C).
Compound I-36: a pale pink solid. Delta H 8.44(s,1H),8.40(t,J＝58.97Hz,1H),7.38–7.28(m,5H),5.78(s,1H),4.86(t,J＝5.48Hz,2H),3.83(s,3H)；δ C 167.75(t,J C-F ＝4.09Hz,1C),154.70,151.37,146.92,137.64,128.84(2C),127.70,127.29(2C),111.77(t,J C-F ＝249.31Hz,1C),106.55,45.20,31.97.
Compound I-37: a pink solid. Delta H 8.48(s,1H),8.44(t,J＝58.99Hz,1H),7.66(m,2H),7.40–7.30(s,8H),5.80(t,J＝4.34Hz,1H),5.65(s,2H),4.87(d,J＝5.48Hz,2H)；δ C 167.70,154.76,151.94,146.91,137.66,137.10,134.51,129.11,128.84,128.54,128.30,127.69,127.30,111.95(t,J C-F ＝249.49Hz,1C),106.70,48.50,45.20.
Compound II-1: white solid. Delta H 8.09(t,J＝58.30Hz,1H),7.34–7.27(m,5H),5.77(s,2H),3.93(s,3H),3.76(s,3H)；δ C 164.56(t,J＝3.55Hz,1C),157.71,157.64,134.57,128.66(2C),128.25,127.85(2C),125.47,124.84,111.52(t,J＝257.65Hz,1C),53.69,53.15,51.11.
Compound II-2: brown solid. Delta H 7.73(t,J＝59.55Hz,1H),7.13(d,J＝2.48Hz,1H),6.91(d,J＝2.36Hz,1H),3.68(s,3H)；δ C 158.39,121.54,113.95,110.39(t,J C-F ＝251.41Hz),36.30.
Compound II-3: yellow liquid. Delta H 7.79(t,J＝59.58Hz,1H),7.15(d,J＝2.51Hz,1H),6.93(d,J＝2.44Hz,1H),4.18(q,J＝7.32Hz,2H),1.41(t,J＝7.32Hz,3H)；δ C 157.45,119.77,114.28,110.33(t,J C-F ＝251.38Hz),44.17,13.97.
Compound II-4: yellow liquid. Delta H 7.79(t,J＝59.59Hz,1H),7.15(d,J＝2.50Hz,1H),6.90(d,J＝2.45Hz,1H),4.17–4.01(m,2H),1.91–1.76(m,2H),0.98(t,J C-F ＝7.42Hz,3H)；δ C 157.83(t,J C-F ＝3.24Hz,1C),120.53,114.06,110.38(d,J＝251.35Hz),50.63,22.04,10.95.
Compound II-5: brown liquid. Delta H 7.85(t,J＝59.63Hz,1H),7.17(d,J＝2.55Hz,1H),6.96(d,J＝2.53Hz,1H),5.24(dt,J＝13.57,6.78Hz,1H),1.41(d,J＝6.80Hz,6H)；δ C 156.92,116.76,114.54,110.19(t,J C-F ＝251.42Hz),50.50,21.64(2C).
Compound II-6: yellow liquid. Delta H 7.76(t,J＝59.62Hz,1H),7.12(t,J＝7.19Hz,1H),6.90(d,J＝2.45Hz,1H),4.10(m,2H),1.75(m,2H),1.34(m,2H),0.93(m,3H)；δ C 157.59(t,J C-F ＝3.21Hz,1C),120.44,113.99,110.28(t,J C-F ＝251.34Hz,1C),48.74,30.58,19.55,13.44.
Compound II-7: brown solid. Delta H 7.98(t,J＝59.83Hz,1H),7.11(d,J＝2.66Hz,1H),7.08(d,J＝2.64Hz,1H),1.88(s,9H)；δ C 159.72,118.51,113.19,110.11(t,J C-F ＝251.48Hz),61.18,28.47(3C).
Compound II-8: yellow liquid. Delta H 7.78(t,J＝59.60Hz,1H),7.14(d,J＝2.47Hz,1H),6.90(d,J＝2.46Hz,1H),4.16–4.03(m,2H),1.91–1.69(m,2H),1.41–1.25(m,6H),0.87(t,J＝6.83Hz,3H)；δ C 157.77,120.44,114.03,110.37(t,J C-F ＝251.37Hz),49.12,31.18,28.60,26.05,22.37,13.86.
Compound II-9: yellow liquid. Delta H 7.79(t,J＝59.60Hz,1H),7.14(d,J＝2.44Hz,1H),6.90(d,J＝2.41Hz,1H),4.16–4.05(m,2H),1.86–1.71(m,2H),1.39–1.16(m,15H),0.86(d,J＝13.65Hz,2H)；δ C 157.80(t,J C-F ＝4.43Hz,1C),120.43,114.03,110.38(t,J C-F ＝251.36Hz),49.13,31.78,29.40,29.34,29.18,29.04,28.65,26.41,22.58,14.01.
Compound II-10: a pink solid. Delta H 7.83(t,J＝59.45Hz,1H),7.62(dd,J＝15.99,8.93Hz,1H),7.19(s,2H),5.32(dd,J＝15.99,2.12Hz,1H),5.14(dd,J＝8.93,2.13Hz,1H)；δ C 159.54,130.43,116.58,115.09,109.92(t,J C-F ＝252.04Hz),104.04.
Compound II-11: yellow liquid. Delta H 7.80(t,J＝59.54Hz,1H),7.16(d,J＝2.54Hz,1H),6.92(d,J＝2.50Hz,1H),5.93(ddt,J＝16.44,10.21,6.16Hz,1H),5.34(ddd,J＝18.02,13.64,0.97Hz,2H),4.77(d,J＝6.15Hz,2H)；δ C 158.39,130.65,120.51,120.13,114.27,110.44(t,J C-F ＝251.57Hz),51.31.
Compound II-12: yellow liquid. Delta H 7.79(t,J＝59.58Hz,1H),7.15(d,J＝2.46Hz,1H),6.90(d,J＝2.42Hz,1H),5.80(ddt,J＝16.87,10.20,6.57Hz,1H),5.06(ddd,J＝13.68,11.17,1.19Hz,2H),4.23–4.05(m,2H),2.14(dd,J＝14.12,7.11Hz,2H),2.02–1.82(m,2H)；δ C 157.99(t,J C-F ＝3.46Hz,1C),136.64,120.56,116.00,114.11,110.39(t,J C-F ＝251.55Hz),48.51,30.36,27.66.
Compound II-13: yellow liquid. Delta H 7.79(t,J＝59.59Hz,1H),7.14(d,J＝2.43Hz,1H),6.90(d,J＝2.38Hz,1H),5.77(ddt,J＝16.93,10.17,6.70Hz,1H),5.00(ddd,J＝13.65,11.05,1.06Hz,2H),4.13(t,J＝7.52Hz,2H),2.11(q,J＝7.08Hz,2H),1.90–1.73(m,2H),1.46(dt,J＝15.02,7.45Hz,2H)；δ C 157.94,137.77,120.39,115.25,114.13,110.40(d,J C-F ＝251.41Hz),48.92,33.04,28.07,25.60.
Compound II-14: yellow liquid. Delta H 7.81(t,J＝59.45Hz,1H),7.18(d,J＝2.57Hz,1H),7.07(d,J＝2.53Hz,1H),5.52(s,2H),3.42(s,3H)；δ C 159.49(t,J C-F ＝3.75Hz,1C),119.70,114.76,110.13(t,J C-F ＝251.89Hz),79.10,57.61.
Compound II-15: brown solid. Delta H 7.68(t,J＝59.25Hz,1H),7.24(d,J＝2.62Hz,1H),7.15(d,J＝2.57Hz,1H),5.14(s,2H)；δ C 160.89(t,J C-F ＝2.48Hz,1C),119.46,115.33,112.71,110.29(t,J C-F ＝253.1Hz),36.54.
Compound II-16: yellow liquid. Delta H 7.73(t,J＝59.48Hz,1H),7.17(d,J＝2.57Hz,1H),7.01(d,J＝2.52Hz,1H),4.96(s,2H),4.26(q,J＝7.14Hz,2H),1.30(t,J＝7.15Hz,3H)；δ C 166.34,160.29,121.28,114.13,110.48(t,J C-F ＝251.91Hz),62.24,49.54,14.02.
Compound II-17: yellow liquid. Delta H 7.80(t,J＝59.61Hz,1H),7.14(d,J＝2.46Hz,1H),6.86(d,J＝2.40Hz,1H),3.96(d,J＝7.41Hz,2H),2.03–1.85(m,1H),1.78–1.61(m,4H),1.34–1.11(m,4H),1.09–0.95(m,2H)；δ C 158.26,121.37,113.78,110.46(t,J C-F ＝251.51Hz),55.10,36.99,30.42(2C),26.08,25.43(2C).
Compound II-18: yellow liquid. Delta H 7.80(t,J＝59.57Hz,1H),7.33–7.16(m,5H),7.02(d,J＝2.43Hz,1H),6.53(d,J＝2.35Hz,1H),4.36(t,J＝7.29Hz,2H),3.13(t,J＝7.28Hz,2H)；δ C 157.82,137.10,128.89(2C),128.78(2C),126.99,121.05,113.60,110.36(t,J＝251.43Hz),50.67,34.53.
Compound II-19: white solid. Delta H 7.83(t,J＝59.57Hz,1H),7.23(d,J＝8.00Hz,2H),7.18(d,J＝7.95Hz,2H),7.10(d,J＝2.52Hz,1H),6.74(d,J＝2.46Hz,1H),5.28(s,2H),2.35(s,3H)；δ C ＝158.54(t,J C-F ＝2.48Hz,1C),138.64,131.28,129.75(2C),128.59(2C),120.16,114.26,110.49(t,J C-F ＝251.55Hz),52.24,21.13.
Compound II-20: white solid. Delta H 7.83(t,J＝59.56Hz,1H),7.41(d,J＝8.15Hz,2H),7.30(d,J＝8.13Hz,2H),7.12(d,J＝2.55Hz,1H),6.77(d,J＝2.52Hz,1H),6.70(dd,J＝17.60,10.89Hz,1H),5.76(d,J＝17.58Hz,1H),5.32(s,2H),5.28(d,J＝10.90Hz,1H)；δ C 158.78(t,J C-F ＝3.15Hz,1C),138.05,135.96,133.69,128.77(2C),126.84(2C),120.16,114.85,114.37,110.50(t,J C-F ＝251.68Hz),52.14.
Compound II-21: white solid. Delta H 7.81(t,J＝59.51Hz,1H),7.35(d,J＝8.39Hz,2H),7.29(d,J＝8.35Hz,2H),7.14(d,J＝2.40Hz,1H),6.78(d,J＝2.02Hz,1H),5.31(s,2H)；δ C 159.08(t,J C-F ＝3.16Hz,1C),134.72,132.91,129.81(2C),129.28(2C),120.06,114.60,110.50(t,J C-F ＝251.91Hz),51.60.
Compound II-22: brown solid. Delta H 7.81(t,J＝59.51Hz,1H),7.39(d,J＝8.45Hz,2H),7.22(d,J＝8.21Hz,2H),7.15(d,J＝2.26Hz,1H),6.81(d,J＝2.06Hz,1H),5.36(s,2H)；δ C 159.27(t,J C-F ＝3.12Hz,1C),149.37(d,J C-F ＝1.68Hz,1C),133.17,129.93(2C),121.49(2C),120.34(q,J C-F ＝257.85Hz,1C),120.09,114.68,110.53(t,J C-F ＝251.91Hz,1C),51.46.
Compound II-23: brown solid. Delta H 8.21(d,J＝8.69Hz,2H),7.78(t,J＝59.44Hz,1H),7.50(d,J＝8.67Hz,2H),7.20(d,J＝2.51Hz,1H),6.89(d,J＝2.42Hz,1H),5.48(s,2H)；δ C 159.87(t,J C-F ＝3.36Hz,1C),147.91,141.57,128.90(2C),124.19(2C),120.19,115.01,110.50(t,J C-F ＝252.28Hz),51.32.
Compound II-24: white solid. Delta H 8.00–7.71(m,5H),7.55–7.47(m,2H),7.43(dd,J＝8.44,1.68Hz,1H),7.11(d,J＝2.56Hz,1H),6.78(d,J＝2.52Hz,1H),5.49(s,2H)；δ C 158.86(t,J C-F ＝3.10Hz,1C),133.16,133.14,131.76,129.13,127.85,127.74,126.63,125.78,120.23,114.39,110.51(t,J C-F ＝251.72Hz),108.51,52.55.
Compound II-25: white solid. Delta H 7.85(t,J＝59.56Hz,1H),7.61–7.56(m,4H),7.49–7.39(m,4H),7.37(t,J＝7.35Hz,1H),7.14(d,J＝2.44Hz,1H),6.83(d,J＝2.36Hz,1H),5.38(s,2H)；δ C 158.83,141.63,140.19,133.26,129.93(2C),128.81(2C),127.74(2C),127.60,127.01(2C),120.24,114.40,110.51(t,J C-F ＝251.74Hz),52.07.
Compound ii-26: yellow solid. Delta H 8.41(s,1H),7.77(m,2H),7.33(d,J＝8.25Hz,1H),7.17(d,J＝2.56Hz,1H),6.88(d,J＝2.51Hz,1H),5.36(s,2H)；δ C 159.57(t,J C-F ＝3.39Hz,1C),151.97,149.19,139.02,129.43,124.71,120.94,114.98,110.44(t,J C-F ＝252.31Hz,1C),48.85.
Compound II-27: brown solid. Delta H 7.75(t,J＝59.48Hz,1H),7.64(s,1H),7.18(d,J＝2.51Hz,1H),6.97(d,J＝2.42Hz,1H),5.47(s,2H)；δ C 159.05(t,J C-F ＝3.34Hz,1C),153.93,141.40,133.44,119.68,114.98,110.33(t,J C-F ＝252.36Hz,1C),44.80.
Compound II-28: brown solid. Delta H 7.97–7.67(m,2H),7.31–7.26(m,2H),7.19–7.14(m,1H),6.98(d,J＝2.49Hz,1H)；δ C 162.65–160.66(d,J C-F ＝251.45Hz,1C),160.88,137.38–137.30(d,J C-F ＝9.19Hz,1C),134.95–134.88(d,J C-F ＝8.52Hz,1C),121.59,119.17–118.99(d,J C-F ＝22.81Hz 1C),118.22–118.02(d,J C-F ＝24.80Hz,1C),116.36–116.32(d,J C-F ＝3.85Hz,1C),114.70,110.52(t,J C-F ＝252.52Hz,1C).
Compound ii-29: yellow liquid. Delta H 7.86(t,J＝59.61Hz,1H),7.43–7.28(m,5H),7.14–7.06(m,1H),6.80–6.71(m,1H),6.46–6.35(m,1H),1.77(d,J＝7.10Hz,3H)；δ C 158.01(t,J C-F ＝3.46Hz,1C),138.62,128.93(2C),128.48,127.09(2C),118.02,114.46,110.36(t,J C-F ＝251.55Hz),56.52,18.83.
Compound II-30: yellow solid. Delta H 8.13(s,1H),7.58(t,J＝59.57Hz,1H),7.49(m,2H),7.40–7.33(m,3H),5.48(s,2H)；δ C 160.99(t,J C-F ＝2.77Hz,1C),136.63,133.79,128.88(2C),128.77(2C),128.66,109.63(t,J C-F ＝254.57Hz,1C),53.47.
Compound II-31: yellow solid. Delta H 7.83(td,J＝59.60,1.6Hz,1H),7.39–7.32(m,5H),7.11(d,J＝2.58Hz,1H),6.77(t,J＝2.52Hz,1H),5.33(s,1H)；δ C 158.80(t,J C-F ＝3.14Hz,1C),134.34,129.06(2C),128.66,128.49(2C),120.20,114.34,110.50(t,J C-F ＝252.30Hz,1C),52.37.
Compound II-32: yellow solid. Delta H 7.74(t,J＝59.80Hz,1H),7.57–7.48(m,4H),7.43(t,J＝7.20Hz,1H),7.08(d,J＝2.20Hz,1H),6.90(d,J＝2.0Hz,1H)；δ C 164.61,136.78,129.25(2C),128.88,125.90(2C),119.92,112.10,109.17(t,J C-F ＝250.75Hz,1C).
Compound ii-33: brown solid. Delta H 7.93–7.81(m,2H),7.84(t,J＝59.50Hz,1H),7.32(d,J＝2.50Hz,1H),7.06(s,1H),2.66(s,3H).δ C 195.4,161.1,156.6(d,J C-F ＝255.20Hz,1C),139.80(d,J C-F ＝6.00Hz,1C),130.2,128.70(d,J C-F ＝12.40Hz,1C),124.50(d,J C-F ＝3.70Hz,1C),121.80(t,J C-F ＝2.40Hz,1C),116.80(d,J C-F ＝20.50Hz,1C),114.90,110.50(t,J C-F ＝253.20Hz,1C),26.70.
Compound II-34: brown solid. Delta H 9.32(d,J＝8.62Hz,1H),8.80(s,1H),8.14(dd,J＝8.63,2.23Hz,1H),7.92(t,J＝59.48Hz,1H),7.85(d,J＝2.69Hz,1H),7.29(d,J＝2.71Hz,1H)；δ C 158.92(t,J C-F ＝3.49Hz),151.66,145.86(q,J C-F ＝4.08Hz),135.44(q,J C-F ＝3.34Hz),126.32(q,J C-F ＝33.73Hz),122.99(q,J C-F ＝272.55Hz),120.15,118.69,114.75,110.22(t,J C-F ＝252.75Hz).
Compound II-35: white solid. Delta H 8.09(t,J＝58.03Hz,1H),7.45–7.41(m,3H),7.37–7.35(m,2H),7.08(s,1H),5.32(s,2H)；δ C 164.31,133.20,129.41(2C),129.26,128.82(2C),122.83(q,J＝5.0Hz),119.72(q,J＝44.51Hz),118.36(q,J＝268.6Hz),111.52(t,J＝256.5Hz),53.18.
Compound II-36: brown solid. Delta H 8.05(t,J＝58.29Hz,1H),7.29,5.73,3.94,3.80；δ C 164.53,157.76,157.52,134.22,133.11,129.44,128.82,126.00,123.98,111.42(t,J＝257.76Hz,1H),53.80,53.23,50.40.
Compound II-37: as a yellow oil. Delta H 7.78(t,J＝59.61Hz,1H),7.47(d,J＝8.42Hz,1H),7.43(d,J＝2.01Hz,1H),7.33(dd,J＝8.30,1.94Hz,1H),7.28(d,J＝8.41Hz,2H),7.12(d,J＝8.43Hz,2H),7.09(d,J＝2.51Hz,1H),6.95(d,J＝2.43Hz,1H),5.26(dd,J＝8.61,3.60Hz,1H),4.57(dd,J＝14.00,3.61Hz,1H),4.42(d,J＝11.72Hz,1H),4.24(d,J＝11.73Hz,1H),4.20(dd,J＝14.03,8.64Hz,1H)；δ C 159.12,135.43,135.01,134.41,133.82,129.80,129.10,128.74,128.61,127.72,122.30,113.32,110.43(t,J C-F ＝251.61Hz,1C),75.00,70.51,52.70.
Biological Activity assay example
The compound of the present invention shows excellent activity against various pests in the agricultural field. The results of the insecticidal activity measurement are shown in the following examples.
Example 3: evaluation of insecticidal Activity of partial Compounds on Plutella xylostella
The tested insects are lepidoptera plutella xylostella, and sensitive strains are fed indoors. The method takes the larvae of plutella xylostella in the middle and later stages of 3 years as test objects, and the test method is a leaf dipping method.
The operation process comprises the following steps: each sample was accurately weighed, acetone was added to prepare 10g/L of mother liquor, and diluted to 500ppm with an aqueous solution containing 0.5% tween 80. Preparing the clean cabbage leaves into leaf discs by using a puncher with the diameter of 1.0cm, immersing the leaf discs in the liquid medicine, taking out the leaf discs after 10 seconds, naturally airing the leaf discs, and transferring the leaf discs into a clean vessel. And (3) inoculating 3-year middle-and-later-period larvae of plutella xylostella with consistent growth into the vessel, inoculating 10 heads of test insects in each treatment, and raising at a constant temperature of 28 ℃. The control group was treated with an aqueous solution containing an equivalent amount of 0.5% tween 80 acetone, with 3 replicates. After 48 hours the test results were observed and mortality (%) was calculated according to the formula. Mortality (%) =number of dead insects/number of test insects×100%. The test results are shown in Table 1.
Example 4: evaluation of insecticidal Activity of some Compounds against Spodoptera frugiperda
The test insects were spodoptera littoralis and sensitive lines were raised indoors. The test method is a leaf dipping method by taking spodoptera frugiperda 2-year-old terminal larvae as test objects.
The operation process comprises the following steps: each sample was accurately weighed, acetone was added to prepare 10g/L of mother liquor, and diluted to 500ppm with an aqueous solution containing 0.5% tween 80. The clean corn She Zhi is formed into leaf discs by a puncher with the diameter of 1.0cm and immersed in the liquid medicine, taken out after 10 seconds, naturally dried and moved into a clean vessel. And (3) inoculating spodoptera frugiperda 2-year-end larvae with consistent growth into the vessel, inoculating 10 heads of test insects for each treatment, and raising at a constant temperature of 28 ℃. The control group was treated with an aqueous solution of 0.5% tween 80 in equal amounts with 3 replicates. After 48 hours the test results were observed and mortality (%) was calculated according to the formula. Mortality (%) =number of dead insects/number of test insects×100%. The test results are shown in Table 1.
Example 5: evaluation of insecticidal Activity of partial Compounds on Spodoptera exigua
The tested insects are lepidoptera asparagus caterpillar, and sensitive strains are fed indoors. The method takes beet armyworm 1-year middle-period larvae as test objects, and the test method is a leaf dipping method.
The operation process comprises the following steps: each sample was accurately weighed, acetone was added to prepare 10g/L of mother liquor, and diluted to 500ppm with an aqueous solution containing 0.5% tween 80. Preparing the clean cabbage leaves into leaf discs by using a puncher with the diameter of 1.0cm, immersing the leaf discs in the liquid medicine, taking out the leaf discs after 10 seconds, naturally airing the leaf discs, and transferring the leaf discs into a clean vessel. And (3) inoculating 1-year middle-period larvae of asparagus caterpillar with consistent growth into the vessel, inoculating 10 heads of test insects after each treatment, and feeding in a constant-temperature incubator at 28 ℃. The control group was treated with an aqueous solution of 0.5% tween 80 in equal amounts with 3 replicates. After 48 hours the test results were observed and mortality (%) was calculated according to the formula. Mortality (%) =number of dead insects/number of test insects×100%. The test results are shown in Table 1.
Example 6: evaluation of insecticidal Activity of partial Compounds on Spodoptera litura
The tested insects are lepidoptera prodenia litura and are raised into sensitive strains indoors. The test method is a leaf dipping method by taking the larva of prodenia litura at the end stage of 1 age as a test object.
The operation process comprises the following steps: each sample was accurately weighed, acetone was added to prepare 10g/L of mother liquor, and diluted to 500ppm with an aqueous solution containing 0.5% tween 80. Preparing the clean cabbage leaves into leaf discs by using a puncher with the diameter of 1.0cm, immersing the leaf discs in the liquid medicine, taking out the leaf discs after 10 seconds, naturally airing the leaf discs, and transferring the leaf discs into a clean vessel. And (3) inoculating the prodenia litura end-stage larvae with consistent growth into a vessel, inoculating 10 heads of test insects in each treatment, and raising at a constant temperature of 28 ℃. The control group was treated with an aqueous solution of 0.5% tween 80 in equal amounts with 3 replicates. After 48 hours the test results were observed and mortality (%) was calculated according to the formula. Mortality (%) =number of dead insects/number of test insects×100%. The test results are shown in Table 1.
Table 1 test of insecticidal Activity of some of the compounds of the present invention against 4 lepidopteran pests
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The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (4)

1. The N-difluoromethyl azole selenourea derivative is characterized by having the following structural formula:
2. an agropharmaceutically acceptable salt of the N-difluoromethyl azole selenourea derivative, which is a salt formed by the N-difluoromethyl azole selenourea derivative according to claim 1 and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.
3. The use of the N-difluoromethyl selenourea derivative according to claim 1 or the N-difluoromethyl selenourea derivative according to claim 2 in the preparation of a medicament for controlling pests, such as plutella xylostella, spodoptera frugiperda, spodoptera exigua and prodenia litura.
4. The insecticidal composition is characterized by comprising an active component and an agriculturally acceptable carrier, wherein the weight percentage of the active component in the composition is 0.01-99.99%, and the active component is the N-difluoromethyl azole selenourea derivative of claim 1 or the agriculturally acceptable salt of the N-difluoromethyl azole selenourea derivative of claim 2.
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